US4847421A - Palladium-nitrile ligand catalyst system and oxidation processes - Google Patents

Palladium-nitrile ligand catalyst system and oxidation processes Download PDF

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US4847421A
US4847421A US07/149,839 US14983988A US4847421A US 4847421 A US4847421 A US 4847421A US 14983988 A US14983988 A US 14983988A US 4847421 A US4847421 A US 4847421A
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palladium
copper
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ligand
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Janis Vasilevskis
Paul L. Ridgway
Eric R. Evitt
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Catalytica Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/20—Non-coordinating groups comprising halogens
    • B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate

Definitions

  • This invention relates generally to palladium catalyzed oxidations of various hydrocarbons, and more specifically to catalyst systems containing palladium, copper, and a ligand.
  • Palladium catalysts are useful in the oxidation of unsaturated hydrocarbons. Some generalized examples of such reactions are: ##STR1##
  • Wacker-type oxidation process of the prior art uses PdCl 2 /CuCl 2 as the catalyst system where Cu +2 plays the role of the co-catalyst for palladium reoxidation.
  • Chloride (Cl - ) is an essential ingredient since as a Pd +2 ligand, it provides a driving force for reaction (3) and, as a Cu +2 ligand, it makes reaction (4) thermodynamically favorable.
  • the palladium compound can be separately complexed with the olefin, in this instance, ethylene, to form a second complex:
  • the process disclosed is complete when the ethylene, coordinated with the Pd(II) complex, is oxidized with the combined oxygen contained in the oxygen complex, under mild conditions, to produce acetaldehyde.
  • the process is accomplished in two steps. First, oxygen is passed through the reactants to form the oxygen complex. The system is then heated to remove excess oxygen. In the second step, ethylene is introduced and passed through the oxygen complex. The ethylene-palladium complex forms and is oxidized by the oxygen complex at nearly room temperature to obtain acetaldehyde.
  • the present invention consists of a palladium catalyst system which is comprised of PdX 2 and CuY 2 and a ligand L for the palladium and(or) copper.
  • the ligand provides the desired thermodynamics and kinetics to make the total oxidation system functional.
  • a nitrile containing ligand improves the performance of the Wacker chloride system.
  • X and Y are selected independently from the group consisting of BF 4 - , CF 3 COO - , CH 3 COO - , SO 4 .sup. ⁇ and NO 3 - .
  • the ligand is chosen from the group of compounds containing nitrile functionality. Further, a polar solvent, in which the catalyst system is soluble and which itself does not oxidize appreciably, is used as the oxidation medium for the olefin, or more generally, for the nucleophilic addition.
  • the ligand can serve as a reaction medium.
  • Chloride ion is not required.
  • the palladium and copper compounds should be substantially chloride-free.
  • the instant invention shows that other classes of ligand can be substituted for Cl - while providing an efficient oxidation system.
  • One such class of ligands is the nitriles.
  • the reaction scheme shown below depicts but one way in which these ligands might operate in the instant catalytic oxidation. S is used to represent the substrate. ##STR5##
  • the catalyst system of the present invention comprises a palladium component, a copper component and at least one ligand component for the palladium and(or) copper. All three components must be present to generate a catalytic oxidation system. While eliminating chlorides from all components is preferred, it is to be understood by those skilled in the art that chlorides may enter the system as contaminants or artifacts of previous syntheses of the catalyst components. Further, it is recognized that the addition of a nitrile ligand to the Wacker system achieves surprising and unexpected improvements in conversion and selectivity.
  • any substantially chloride-free palladium containing material, or mixtures thereof, which are suitable in catalytic oxidations, can be used in the catalyst system of the present invention.
  • Finely divided palladium powder, palladium metal, and substantially chloride-free palladium compounds are all useful in the present invention, either individually or in combination.
  • the type of palladium counterion employed is important. Electron-withdrawing-counterions make palladium a more potent oxidant. Weakly-bonded-counterions allow the ligand(s) of the catalyst to interact with the palladium. It is conceivable that, in some cases, the counterion can also serve the function of the ligand.
  • the preferred palladium compounds are palladium tetrafluoroborate, Pd(BF 4 ) 2 ; palladium trifluoroacetate, Pd(CF 3 COO) 2 ; palladium sulfate, PdSO 4 ; palladium acetate, Pd(CH 3 COO) 2 ; and palladium nitrate, Pd(NO 3 ) 2 .
  • any substantially chloride-free copper containing material, or mixtures thereof, can be used in the catalyst system of the present invention.
  • Copper metal, cuprous or cupric salts, and even copper of higher oxidation states, can be used as the starting point of the copper component.
  • the type of copper counterion employed is also important. It must not interfere with the palladium oxidation chemistry or with the positive effect of the ligand(s) of the system. In some cases, the counterion might also serve as the ligand.
  • Preferred copper compounds are copper tetrafluoroborate, copper trifluoroacetate, copper sulfate, copper acetate, and copper nitrate.
  • the ligand(s) can be selected to complex palladium and(or) the copper compounds. Their function is to provide favorable thermodynamics and kinetics for the oxidation process.
  • One such class of ligands which is useful in the instant invention is the nitriles (RC ⁇ N) where R is selected from a great variety of substituents. One is also not limited to mononitriles.
  • the preferred ligand is acetonitrile, where R is equal to CH 3 .
  • R can by any other group that does not interfere with the palladium and copper chemistry and does not affect adversely the properties of the catalyst system.
  • R can be a hydrocarbon or a derivatized hydrocarbon. Non-exhaustive examples are R: ##STR6##
  • hydrocarbon capable of being oxidized by palladium is a substrate for the catalyst system of the instant invention.
  • hydrocarbons are olefins, substituted olefins, aromatics and substituted aromatics.
  • nucleophiles can be employed in the instant invention. They include but are not limited to water, alcohols, amines, and nucleophilic hydrocarbons, e.g. CH 2 (CO 2 R) 2 .
  • the polar solvent of the instant invention is selected to dissolve the catalyst components (copper and palladium salts).
  • the range of polar solvents which are available is indeed quite large, including, but not limited to ketones, alcohols, acids, and aqueous systems.
  • the preferred solvents of the instant invention are water, acetone and propylene carbonate. In some cases the ligand, e.g. acetonitrile, can itself be the preferred solvent.
  • the acidity i.e., pH
  • Various proton sources such as HBF 4 , CF 3 COOH, CH 3 COOH, HNO 3 or H 2 SO 4 can be used. It is preferred to use the acid having the same anion as the copper component of the catalyst system.
  • the oxidation temperatures are typically between 20° C. and 200° C., preferrably 45°-90° C. At lower temperatures, the rate of oxidation becomes too slow. At higher temperatures, overoxidation can be a problem. If the ligand of the catalyst system is a nitrile, then the upper temperature limit (which depends on the pH and amount of water present) may depend upon where nitrile hydrolysis to an amide begins.
  • the operating pressure for the oxidation is typically between 0-200 psig. At lower pressures, the rate of oxidation can be too slow, while at higher pressures the risks of overoxidation and explosion increase.
  • the acidity of the liquid phase has to be controlled for maximum oxidation activity and selectivity to the desired product. It has to be adjusted on a case-by-case basis.
  • the ratio of palladium to copper can vary between 1/1 to 1/500 depending on how efficiently the copper catalyst reoxidizes the palladium catalyst. The slower the reoxidation, the more copper is required.
  • a preferred ratio of palladium to copper is in the range of 1/5 to 1/50 depending on the counterion that is used.
  • the amount of ligand present can vary from molar amounts equivalent to the palladium and(or) copper molar amounts to a large excess, i.e., solvent for the reaction.
  • solvent for the reaction i.e., solvent for the reaction.
  • oxidation proceeds well when the nitrile represents 10-20% of the total solvent.
  • one would like to use the minimum amount of nitrile necessary to get the desired reaction rate because this reduces the cost of the catalyst system and increases the ease of separation of the catalyst and the product.
  • Reaction times vary from a few minutes to 48 hours. Short reaction times can lead to heat management problems while long reaction times lead to economically unattractive large reactor sizes.
  • the reaction vessel utilized was either (a) an 80 ml Fischer-Porter® (Fischer-Porter Co., Warminster, Pa.) bottle having a magnetic stirrer capable of 250 rpm (hereinafter referred to as R1), (b) an 80 ml Fischer-Porter® bottle with a motor driven titanium paddle stirrer (1750 rpm) (hereinafter referred to as R2), or (c) a 100 ml Fluitron SS316 reactor (5000 psi rating) with a conventional stirrer (2500 rpm maximum) (hereinafter referred to as R3).
  • R1 an 80 ml Fischer-Porter®
  • R2 motor driven titanium paddle stirrer
  • R1's were fitted with a pressure gage, oxygen inlet line, vent line, and a liquid injection port through which liquid (e.g., olefin) could be injected at any desired operating temperature and pressure.
  • Each R1 used a 3" long, 11/2" diameter Teflon® (DuPont Co., Wilmington, Del. coated stirring bar.
  • the oxygen lines to the reactors were fitted with filters and check valves.
  • the R1's were heated in a glycol bath whose temperature was controlled by a I 2 R Thermo-Watch. Each bath was protected from inadvertent overheating by an I 2 R Over-Temp Probe.
  • R2's were outfitted in a similar fashion as the R1's, the major difference being the mode of stirring, i.e., the motor driven two blade paddle stirrer. Both the stirrer shaft and paddle were made of titanium so that comparison runs using corrosive concentrations of chloride could be carried out.
  • R3 was a 100 ml reactor manufactured by Fluitron Inc. of Warminster, Pa.
  • the double disk six pitched blade stirrer was originally designed to circulate the catalyst solution out of and into the reactor so that the reactor need not be depressurized for sampling.
  • R3 was heated by an electrical heater.
  • the temperature was monitored by a thermocouple.
  • the temperature was set using a RI Instruments controller and was monitored on an Analog Devices Digital Thermometer.
  • a Watlow over-heat monitor was used to shut off the whole system. Representative samples could be taken using a pressure syringe while R3 was in full operation.
  • the reactors were quenched to room temperature and were depressurized.
  • One phase solutions could be analyzed directly by GC.
  • the reactions using water required extraction of the products before GC analysis could be performed.
  • conversion is defined as the moles of olefin reacted per mole of olefin fed;
  • selectiveivity is defined as the moles of ketone produced per mole of olefin reacted;
  • yield is defined as the product of selectivity and conversion; and
  • turnover per Pd is defined as the moles of ketone produced per mole of Pd present in the system.
  • Example V did not use a nitrile ligand. One observes a single turnover on palladium, i.e., the palladium did not reoxidize and no further product was formed. In Examples VI to X, catalytic activity persisted until all of the olefin (1-, 2-, and 3-hexene) was oxidized to ketones (see footnote 3 in Table 2).
  • Example XIX-XXI further illustrates that the addition of a ligand, specifically acetonitrile, improves the results obtained in conventional Wacker systems.
  • a ligand specifically acetonitrile
  • Common values for conversion and selectivity in the Wacker system without a ligand are 57.4 and 61.3. With acetonitrile present as a ligand these values increase to 94.3 and 85.1, respectively.

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Abstract

A substantially chloride-free palladium oxidation system, comprising a palladium component, a copper component, and a ligand is described. The Wacker system, consisting of palladium and copper chlorides is also improved by the addition of a ligand. The palladium and copper counterion are independently selected from BF4-, CF3COO-, CH3COO-, SO4=, and NO3-. The ligand is preferably a nitrile-containing compound.

Description

This is a divisional of application Ser. No. 07/089,003 filed Aug. 21, 1987, now U.S. Pat. No. 4,738,943, which is a file wrapper continuation of application Ser. No. 06/826,078 filed Feb. 4, 1986, and now abandoned.
DESCRIPTION
1. Technical Field
This invention relates generally to palladium catalyzed oxidations of various hydrocarbons, and more specifically to catalyst systems containing palladium, copper, and a ligand.
2. Background of the Invention
Palladium catalysts are useful in the oxidation of unsaturated hydrocarbons. Some generalized examples of such reactions are: ##STR1##
In the reactions outlined above, Pd+2 is reduced. The overall reaction is made catalytic if the palladium can be reoxidized by an oxidizing agent. Preferentially, one would use plentiful and cheap oxygen from air. The direct reoxidation of palladium by oxygen is thermodynamically possible but kinetically too slow. As a result, a co-catalyst is required to speed up the overall oxidation process.
The Wacker-type oxidation process of the prior art uses PdCl2 /CuCl2 as the catalyst system where Cu+2 plays the role of the co-catalyst for palladium reoxidation.
Pd°+2CuCl.sub.4.sup.-2 →PdCl.sub.4.sup.-2 +2CuCl.sub.2.sup.-( 3)
2Cl.sup.- +2HCl+1/2O.sub.2 +2CuCl.sub.2.sup.- →2CuCl.sub.4.sup.-2 +H.sub.2 O                                                (4)
It should be noted that the copper is necessary to improve palladium reoxidation kinetics. Chloride (Cl-) is an essential ingredient since as a Pd+2 ligand, it provides a driving force for reaction (3) and, as a Cu+2 ligand, it makes reaction (4) thermodynamically favorable.
The above Wacker system, however, presents several substantial engineering problems making commercial application difficult. High chloride concentrations result in severe corrosion, requiring the use of expensive, i.e. titanium clad, reactor vessels. Further, the presence of chloride ions results in the formation of undesirable chlorinated byproducts which lowers the overall yield of desired material. In addition, these chlorinated by-products often prove difficult to separate from the desired product.
In response to these unfavorable characteristics of Wacker-type catalysts, new systems have been developed by others to reduce the level of chloride present in the olefin oxidation. Examples of the use of polyoxoanions to reduce chloride levels in these types of systems may be found in Belgian Pat. No. 828,603, the work of Ogawa et. al., J.C.S. Chem. Comm., 1274-75 (1981), and U.S. Pat. No. 4,434,082.
Another approach to the problems presented by the Wacker systems has been to increase oxidation kinetics so lower temperatures and lower pressures can be employed, mitigating to a certain extent the harsh conditions of Wacker systems. In U.S. Pat. No. 4,521,631, it is disclosed that a stable oxygen complex of Cu(I)Cl with hexamethylphosphoramide (hmpa) can be formed:
2Cu(I)Cl+2hmpa+O.sub.2 →[(Cu(I)Cl hmpa)].sub.2 O.sub.2 ( 5)
These oxygen complexes are extremely stable. It is further disclosed that the palladium compound can be separately complexed with the olefin, in this instance, ethylene, to form a second complex:
Pd(II)Cl.sub.2 +2hmpa→Pd(II)Cl.sub.2 (hmpa).sub.2   ( 6)
Pd(II)Cl.sub.2 (hmpa).sub.2 +CH.sub.2 ═CH.sub.2 →Pd(II)Cl.sub.2 (C.sub.2 H.sub.4)(hmpa)+hmpa                              (7)
The process disclosed is complete when the ethylene, coordinated with the Pd(II) complex, is oxidized with the combined oxygen contained in the oxygen complex, under mild conditions, to produce acetaldehyde. The process is accomplished in two steps. First, oxygen is passed through the reactants to form the oxygen complex. The system is then heated to remove excess oxygen. In the second step, ethylene is introduced and passed through the oxygen complex. The ethylene-palladium complex forms and is oxidized by the oxygen complex at nearly room temperature to obtain acetaldehyde.
While the above described system may affect a reduction in corrosion of equipment and by-product formation which result from chlorides, the process is complex, requiring two distinct processing steps. The instant invention teaches a way to accomplish similar reactions, chloride-free, in a simple one step process. It is therefore an object of this invention to provide a process for olefin oxidation, as well as general nucleophilic addition, which eliminates the chlorides of Wacker systems while retaining commercially acceptable levels of substrate conversion and product selectivity.
It is a further object of this invention to provide a process in which substrate oxidation can be accomplished in a single step.
It is a further object of this invention to provide a palladium catalyst and its reoxidation system which is simple and inexpensive.
It is another object of this invention to provide an improved Wacker system wherein the addition of the ligand component greatly improves conversion and selectivity.
These and other advantages will be made apparent to those skilled in the art from the specifications and claims which follow.
SUMMARY OF THE INVENTION
The present invention consists of a palladium catalyst system which is comprised of PdX2 and CuY2 and a ligand L for the palladium and(or) copper. In a similar, but not necessarily identical manner to chloride in the prior art Wacker system, the ligand provides the desired thermodynamics and kinetics to make the total oxidation system functional. In one embodiment, a nitrile containing ligand improves the performance of the Wacker chloride system.
X and Y are selected independently from the group consisting of BF4 -, CF3 COO-, CH3 COO-, SO4.sup.═ and NO3 -. The ligand is chosen from the group of compounds containing nitrile functionality. Further, a polar solvent, in which the catalyst system is soluble and which itself does not oxidize appreciably, is used as the oxidation medium for the olefin, or more generally, for the nucleophilic addition. The ligand can serve as a reaction medium.
Chloride ion is not required. In the preferred embodiment, the palladium and copper compounds should be substantially chloride-free.
DETAILED DESCRIPTION OF THE INVENTION
It has been previously recognized that the major rate limitation in the palladium-catalyzed oxidation of olefins is the reoxidation of palladium with a cheap reoxidant like air or oxygen.
An example is shown in equation (8). ##STR2##
The prior art Wacker system addresses the critical palladium reoxidation limitation by the use of Cu+2 and large amounts of chloride. Equations 3 and 4 are described above in the Background of the Invention. ##STR3##
In the Wacker system the chloride ion is a counterion for both palladium and copper and, at the same time, a ligand. These interactions provide the driving force for reactions (3) and (4). Furthermore, it was thought that Cl- was also unique in that it could provide a pathway for electron transfer by bridging between copper and palladium. ##STR4##
The instant invention, for the first time, shows that other classes of ligand can be substituted for Cl- while providing an efficient oxidation system. One such class of ligands is the nitriles. The reaction scheme shown below depicts but one way in which these ligands might operate in the instant catalytic oxidation. S is used to represent the substrate. ##STR5##
The overall transformation [equation (13)] is simple while the actual catalytic cycle can be quite complex [equations (10) to (12)]. Thus, there exists a delicate balance between the various transformations which can change depending on the anion(s), the nitrile(s) and specific reaction conditions, e.g. pH, O2 pressure, etc.
A. Catalyst System
The catalyst system of the present invention comprises a palladium component, a copper component and at least one ligand component for the palladium and(or) copper. All three components must be present to generate a catalytic oxidation system. While eliminating chlorides from all components is preferred, it is to be understood by those skilled in the art that chlorides may enter the system as contaminants or artifacts of previous syntheses of the catalyst components. Further, it is recognized that the addition of a nitrile ligand to the Wacker system achieves surprising and unexpected improvements in conversion and selectivity. Thus, while the preferred embodiments of the present invention refer to substantially chloride-free catalyst systems which term is used to indicate the possible presence of chloride only as a contaminant, the use of nitrile-ligands with Wacker type catalyst systems, containing chloride, is intended to be within the scope of the claims.
(1) Palladium Component
In the preferred embodiment, any substantially chloride-free palladium containing material, or mixtures thereof, which are suitable in catalytic oxidations, can be used in the catalyst system of the present invention. Finely divided palladium powder, palladium metal, and substantially chloride-free palladium compounds are all useful in the present invention, either individually or in combination. If palladium compounds are used, the type of palladium counterion employed is important. Electron-withdrawing-counterions make palladium a more potent oxidant. Weakly-bonded-counterions allow the ligand(s) of the catalyst to interact with the palladium. It is conceivable that, in some cases, the counterion can also serve the function of the ligand. The preferred palladium compounds are palladium tetrafluoroborate, Pd(BF4)2 ; palladium trifluoroacetate, Pd(CF3 COO)2 ; palladium sulfate, PdSO4 ; palladium acetate, Pd(CH3 COO)2 ; and palladium nitrate, Pd(NO3)2.
(2) Copper Component
In the preferred embodiment, any substantially chloride-free copper containing material, or mixtures thereof, can be used in the catalyst system of the present invention. Copper metal, cuprous or cupric salts, and even copper of higher oxidation states, can be used as the starting point of the copper component. The type of copper counterion employed is also important. It must not interfere with the palladium oxidation chemistry or with the positive effect of the ligand(s) of the system. In some cases, the counterion might also serve as the ligand. Preferred copper compounds are copper tetrafluoroborate, copper trifluoroacetate, copper sulfate, copper acetate, and copper nitrate.
(3) Ligand(s)
The ligand(s) can be selected to complex palladium and(or) the copper compounds. Their function is to provide favorable thermodynamics and kinetics for the oxidation process. One such class of ligands which is useful in the instant invention is the nitriles (RC≡N) where R is selected from a great variety of substituents. One is also not limited to mononitriles. The preferred ligand is acetonitrile, where R is equal to CH3. R can by any other group that does not interfere with the palladium and copper chemistry and does not affect adversely the properties of the catalyst system. R can be a hydrocarbon or a derivatized hydrocarbon. Non-exhaustive examples are R: ##STR6##
While the preferred embodiment has been described with reference to substantially chloride-free components, the addition of nitrile-ligand components to the chloride-containing Wacker system is specifically intended to be within the scope of this invention and appended claims.
B. Hydrocarbon Oxidation Process
In addition to the previously described utility of the instant oxidation catalyst system in the oxidation of olefins to ketones, it is also useful in any other hydrocarbon oxidation in which palladium changes its oxidation state, e.g. Pd+2 →Pd°, Pd+4 →Pd+2. A generalized example involving a hydrocarbon RH and an organic nucleophile NuH is represented by Equation (14).
RH+NuH+Pd.sup.+n →RNu+Pd.sup.+n-2 +2H.sup.+         ( 14)
Specific examples of these types of reactions, involving oxidative carbonylation and a coupling reaction, are shown in Equations (15) and (16), respectively. However, other known hydrocarbon oxidation reactions are intended to be within the scope of the appended claims. ##STR7##
(1) Hydrocarbon Substrate
Any hydrocarbon capable of being oxidized by palladium is a substrate for the catalyst system of the instant invention. Specific, nonlimiting examples of such hydrocarbons are olefins, substituted olefins, aromatics and substituted aromatics.
(2) Nucleophiles
A large variety of nucleophiles can be employed in the instant invention. They include but are not limited to water, alcohols, amines, and nucleophilic hydrocarbons, e.g. CH2 (CO2 R)2.
(3) Solvent
The polar solvent of the instant invention is selected to dissolve the catalyst components (copper and palladium salts). The range of polar solvents which are available is indeed quite large, including, but not limited to ketones, alcohols, acids, and aqueous systems. The preferred solvents of the instant invention are water, acetone and propylene carbonate. In some cases the ligand, e.g. acetonitrile, can itself be the preferred solvent.
(4) Acid
Since the various steps involved in the overall oxidation are acid dependent, the acidity, i.e., pH, has to be adjusted for maximum performance. Various proton sources such as HBF4, CF3 COOH, CH3 COOH, HNO3 or H2 SO4 can be used. It is preferred to use the acid having the same anion as the copper component of the catalyst system.
(5) Oxygen
Depending on the process one can use either air or oxygen. Other known sources of oxygen are acceptable but would be less economical. Similarly, other known oxidants would be acceptable but are anticipated to be less economical.
(6) Process Conditions
The oxidation temperatures are typically between 20° C. and 200° C., preferrably 45°-90° C. At lower temperatures, the rate of oxidation becomes too slow. At higher temperatures, overoxidation can be a problem. If the ligand of the catalyst system is a nitrile, then the upper temperature limit (which depends on the pH and amount of water present) may depend upon where nitrile hydrolysis to an amide begins.
The operating pressure for the oxidation is typically between 0-200 psig. At lower pressures, the rate of oxidation can be too slow, while at higher pressures the risks of overoxidation and explosion increase.
The acidity of the liquid phase has to be controlled for maximum oxidation activity and selectivity to the desired product. It has to be adjusted on a case-by-case basis.
The ratio of palladium to copper can vary between 1/1 to 1/500 depending on how efficiently the copper catalyst reoxidizes the palladium catalyst. The slower the reoxidation, the more copper is required. A preferred ratio of palladium to copper is in the range of 1/5 to 1/50 depending on the counterion that is used.
The amount of ligand present can vary from molar amounts equivalent to the palladium and(or) copper molar amounts to a large excess, i.e., solvent for the reaction. In the case of acetonitrile, oxidation proceeds well when the nitrile represents 10-20% of the total solvent. In general one would like to use the minimum amount of nitrile necessary to get the desired reaction rate because this reduces the cost of the catalyst system and increases the ease of separation of the catalyst and the product.
Reaction times vary from a few minutes to 48 hours. Short reaction times can lead to heat management problems while long reaction times lead to economically unattractive large reactor sizes.
This invention can be more fully understood by reference to the following examples.
In all the oxidations that are described in the following examples I-XXI, the reaction vessel utilized was either (a) an 80 ml Fischer-Porter® (Fischer-Porter Co., Warminster, Pa.) bottle having a magnetic stirrer capable of 250 rpm (hereinafter referred to as R1), (b) an 80 ml Fischer-Porter® bottle with a motor driven titanium paddle stirrer (1750 rpm) (hereinafter referred to as R2), or (c) a 100 ml Fluitron SS316 reactor (5000 psi rating) with a conventional stirrer (2500 rpm maximum) (hereinafter referred to as R3). The observed relative oxidation rates, because of increased mass transport of oxygen and (or) olefin, can increase substantially in going from R1→R2→R3.
R1's were fitted with a pressure gage, oxygen inlet line, vent line, and a liquid injection port through which liquid (e.g., olefin) could be injected at any desired operating temperature and pressure. Each R1 used a 3" long, 11/2" diameter Teflon® (DuPont Co., Wilmington, Del. coated stirring bar. The oxygen lines to the reactors were fitted with filters and check valves. The R1's were heated in a glycol bath whose temperature was controlled by a I2 R Thermo-Watch. Each bath was protected from inadvertent overheating by an I2 R Over-Temp Probe.
R2's were outfitted in a similar fashion as the R1's, the major difference being the mode of stirring, i.e., the motor driven two blade paddle stirrer. Both the stirrer shaft and paddle were made of titanium so that comparison runs using corrosive concentrations of chloride could be carried out.
R3 was a 100 ml reactor manufactured by Fluitron Inc. of Warminster, Pa. The double disk six pitched blade stirrer was originally designed to circulate the catalyst solution out of and into the reactor so that the reactor need not be depressurized for sampling. R3 was heated by an electrical heater. The temperature was monitored by a thermocouple. The temperature was set using a RI Instruments controller and was monitored on an Analog Devices Digital Thermometer. A Watlow over-heat monitor was used to shut off the whole system. Representative samples could be taken using a pressure syringe while R3 was in full operation.
All reactors were first loaded with the solvent followed by addition of the various catalyst components. The reactor was sealed and pressurized/depressurized at least four times with oxygen. The final pressure was left at 80 psig. The reactor was then heated to the reaction temperature. The olefin was injected using a pressure syringe without the need for depressurizing. Oxygen could be supplied by repressurizing as the pressure fell or by leaving the oxygen supply line open to a constant pressure source of the gas.
In R1 and R2 oxidation runs, samples could not be obtained during a run. In R3 reactions, uniform samples could be obtained as a function of time.
After the desired reaction time, the reactors were quenched to room temperature and were depressurized. One phase solutions could be analyzed directly by GC. The reactions using water required extraction of the products before GC analysis could be performed.
In the following examples, "conversion" is defined as the moles of olefin reacted per mole of olefin fed; "selectivity" is defined as the moles of ketone produced per mole of olefin reacted; "yield" is defined as the product of selectivity and conversion; and "turnover per Pd" is defined as the moles of ketone produced per mole of Pd present in the system.
C. WORKING EXAMPLES Examples I to IV
A series of 1-hexene oxidations were carried out using various nitrile-polar solvent mixtures. Table 1 lists the reaction conditions and the results. These oxidation runs demonstrate that the catalyst systems of the instant invention can be used in a variety of nitrile-polar solvent combinations. The results further demonstrate that one can obtain high conversions of olefin with good selectivity to either a mixture of ketones (2- and 3-hexanone) or pure ketone (2-hexanone). It should be noted that in the initial stages of the reaction, the main side products are isomers of 1-hexene, i.e., 2- and 3-hexene which, with time, are converted to a mixture of 2- and 3-hexanone. Thus if the reactions are run to full conversion, one gets very high yields of ketone product.
EXAMPLES V to X
A series of 1-hexene oxidations were carried out using various ratios of polar solvent to nitrile.
Example V did not use a nitrile ligand. One observes a single turnover on palladium, i.e., the palladium did not reoxidize and no further product was formed. In Examples VI to X, catalytic activity persisted until all of the olefin (1-, 2-, and 3-hexene) was oxidized to ketones (see footnote 3 in Table 2).
The oxidation runs in Table 2 demonstrate that a ligand is needed for catalytic oxidation. Further, these runs demonstrate that various ratios of ligand to solvent are effective as is the ligand when it is used as a solvent.
Examples XI to XXI
A series of 1-hexene oxidations were carried out using various counterions for the palladium and copper components of the catalyst. Table 3 lists the reaction conditions and the results.
These oxidation runs demonstrate that a large variety of counterions or counterion mixtures can be useful in the instant catalyst system. High conversion of 1-hexene to high yields of 2-hexanone or ketones (2- and 3-hexanone) can be obtained. The anion can be used to control the composition of the final product.
Table 3, Example XIX-XXI, further illustrates that the addition of a ligand, specifically acetonitrile, improves the results obtained in conventional Wacker systems. Common values for conversion and selectivity in the Wacker system without a ligand are 57.4 and 61.3. With acetonitrile present as a ligand these values increase to 94.3 and 85.1, respectively.
                                  TABLE 1                                 
__________________________________________________________________________
Oxidation of 1-Hexene in Various Nitrile/Solvent Systems                  
__________________________________________________________________________
Examples I to IV                                                          
                                        % Con-          Turnovers         
                 Ratio of                                                 
                      Pd.sup.+2 Cu.sup.+2                                 
                                        version         per               
                 Solvent    Wt.     Wt. of   % Selectivity                
                                                        Pd per min.       
Run #                                                                     
    Reactor                                                               
         Solvent CH.sub.3 CN                                              
                      Anion (gm)                                          
                                Anion                                     
                                    (gm)                                  
                                        1-Hexene                          
                                             Ketones                      
                                                  2-Hexanone              
                                                        (2-Hexanone)      
__________________________________________________________________________
I   R2   H.sub.2 O                                                        
                 9    CF.sub.3 COO.sup.-                                  
                            0.05                                          
                                SO.sub.4.sup.═                        
                                    4.5 77.1 90.4 89.9  0.61              
II  R1                                                                    
          ##STR8##                                                        
                 9    CF.sub.3 COO.sup.-                                  
                            0.281                                         
                                BF.sub.4.sup.-                            
                                    1.227                                 
                                        100  73.9 45.4  --                
III R1                                                                    
          ##STR9##                                                        
                 9    CF.sub.3 COO.sup.-                                  
                            0.281                                         
                                BF.sub.4.sup.-                            
                                    1.227                                 
                                        100  89.4 50.4  --                
IV  R1                                                                    
          ##STR10##                                                       
                 9    CF.sub.3 COO.sup.-                                  
                            0.281                                         
                                BF.sub.4.sup.-                            
                                    1.227                                 
                                        100  15.6 10.1  --                
__________________________________________________________________________
Reaction Conditions                                                       
Run #                                                                     
    Reactor                                                               
          T (°C.)                                                  
               P (O.sub.2) (psi) gage                                     
                         Time (hr)                                        
                                RCN + Solvent (ml)                        
                                            RCN R.sup.═               
                                                   Olefin                 
                                                          RPM)            
__________________________________________________________________________
I   R2    85   85        2      16.5        CH.sub.3                      
                                                   2      1750            
II  R1    60   85        5      30          CH.sub.3                      
                                                   2      250             
III R1    60   85        5.25   30          CH.sub.3                      
                                                   2      250             
IV  R1    61   80        5      30          φ  2      250             
__________________________________________________________________________

                                  TABLE 2                                 
__________________________________________________________________________
Oxidation of 1-Hexene as a Function of Acetonitrile Concentration.sup.1   
 Examples V to X                                                          
          ##STR11##                                                       
                Pd.sup.+2  Cu.sup.+2                                      
                                    Time                                  
                                       % Conversion                       
                                               % Selectivity              
                                                       %                  
                                                      Selectivity.sup.3   
Run #    CH.sub.3 CN                                                      
               Anion Wt. (gm)                                             
                          Anion                                           
                              Wt. (gm)                                    
                                   (hr)                                   
                                      of 1-Hexene                         
                                              to 2-Hexanone               
                                                      to                  
__________________________________________________________________________
                                                      Ketones             
V        .sup. 00.sup.4                                                   
               CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   8  99.0    5.3     5.3                 
VI       99    CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   4  98.8    8.7     13.6                
VII      19    CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   4  100     28.7    46.6                
VIII      9    CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   4  96.7    39.8    64.2                
IX        4    CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   6.5                                    
                                      100     49.1    80.1                
X        .sup. CF.sub.3 COO.sup.-                                         
                     .281 BF.sub.4.sup.-                                  
                              1.227                                       
                                   8  100     53.4    91.2                
__________________________________________________________________________
 .sup.1 Reaction conditions: 60° C., 80 psi O.sub.2 (gage), 30 ml  
 volume of solvents, 2 ml olefin.                                         
 .sup.2 Volume ratio.                                                     
 .sup.3 At this point, most of the other products are internal olefins    
 which continue to oxidize. At longer reaction times, the final selectivit
 to 2 and 3hexanone is between 92% and 98%. Does not apply to example V.  
 .sup.4 No acetonitrile was present  only acetone.                        
 .sup.5 No acetone was present  only acetonitrile.                        

                                  TABLE 3                                 
__________________________________________________________________________
Oxidation of 1-Hexene as a Function of the Palladium and Copper           
Counterions                                                               
__________________________________________________________________________
Examples XI to XXI                                                        
           Pd.sup.+2                                                      
                    Cu.sup.+2                                             
                 Wt.      Wt. Time                                        
                                 % Conversion                             
                                         % Selectivity to                 
                                                 % Selectivity            
Run #                                                                     
     Reactor                                                              
           Anion (gm)                                                     
                    Anion (gm)                                            
                              (hr)                                        
                                 of 1-Hexene                              
                                         2-Hexanone                       
                                                 to Ketones               
__________________________________________________________________________
XI   R1    BF.sub.4.sup.-                                                 
                 .375                                                     
                    BF.sub.4.sup.-                                        
                          1.227                                           
                              4.75                                        
                                 100     52.2    88.2                     
XII  R1    CF.sub.3 COO.sup.-                                             
                 .281                                                     
                    BF.sub.4.sup.-                                        
                          1.227                                           
                              5  100     45.9    74.8                     
XIII R1    CF.sub.3 COO.sup.-                                             
                 .281                                                     
                    CF.sub.3 COO.sup.-                                    
                          1.018                                           
                              8  100     40.0    42.1                     
XIV  R2    CF.sub.3 COO.sup.-                                             
                 .050                                                     
                    SO.sub.4.sup.═                                    
                          4.50                                            
                              1  77.1    89.9    90.4                     
XV   R3    CF.sub.3 COO.sup.-                                             
                 .121                                                     
                    SO.sub.4.sup.═                                    
                          10.9                                            
                              1  97.8    70.1    70.1                     
XVI  R2    CH.sub.3 COO.sup.-                                             
                 .250                                                     
                    CH.sub.3 COO.sup.-                                    
                          2.25                                            
                              5.7                                         
                                 95.5    93.1    93.1                     
XVII R2    SO.sub.4.sup.═                                             
                 .126                                                     
                    SO.sub.4.sup.═                                    
                          4.50                                            
                              1  82.4    95.8    96.1                     
XVIII                                                                     
     R1    NO.sub. 3.sup.-                                                
                 .240                                                     
                    NO.sub.3.sup.-                                        
                          0.817                                           
                              2  100     12.3    15.4                     
XIX  R1    Cl.sup.-                                                       
                 .150                                                     
                    Cl.sup.-                                              
                          0.600                                           
                              2.5                                         
                                 100     89.2    89.2                     
XX   R1    Cl.sup.-                                                       
                 .150                                                     
                    Cl.sup.-                                              
                          0.600                                           
                              1  94.3    85.1    85.1                     
XXI  R1    Cl.sup.-                                                       
                 .150                                                     
                    Cl.sup.-                                              
                          0.600                                           
                              1  57.4    61.3    61.3                     
__________________________________________________________________________
Reaction Conditions                                                       
          T   P (O.sub.2)                                                 
                     Time         Solvent                                 
                                        Total Vol.                        
                                               Olefin                     
Run #                                                                     
     Reactor                                                              
          (°C.)                                                    
              (psi) gage                                                  
                     (hr)                                                 
                         Solvents Ratio (ml)   (ml) RPM                   
__________________________________________________________________________
XI   R1   60  85     4.75                                                 
                          ##STR12##                                       
                                  9/1   30     2.0  250                   
XII  R1   60  80     5.0                                                  
                          ##STR13##                                       
                                  9/1   30     2.0  250                   
XIII R1   60  80     8.0                                                  
                          ##STR14##                                       
                                  9/1   30     2.0  250                   
XIV  R2   85  85     0.67                                                 
                         H.sub.2 O/CH.sub.3 CN                            
                                  10.7/1                                  
                                        16     2.0  1750                  
XV   R3   85  85     1.9 H.sub.2 O/CH.sub.3 CN                            
                                  10/1  40     4.8  2000                  
XVI  R2   62  85     2.5 H.sub.2 O/CH.sub.3 CN                            
                                  4/1   16.5   2.0  1000                  
          85         3.2                                                  
XVII R2   87  85     1.0 H.sub.2 O/CH.sub.3 CN                            
                                  10.7/1                                  
                                        16     2.0  1750                  
XVIII                                                                     
     R1   58  85     2.0                                                  
                          ##STR15##                                       
                                  9/1   30     2.0  250                   
XIX  R1   60  85     2.5                                                  
                          ##STR16##                                       
                                  19/1  30     2.0  250                   
XX   R1   60  85     1.0                                                  
                          ##STR17##                                       
                                  19/1  16.5   2.0  250                   
XXI  R1   60  85     1.0                                                  
                          ##STR18##                                       
                                  ∞                                 
                                        16.5   2.0  250                   
__________________________________________________________________________

Claims (12)

We claim:
1. A process for the oxidation of a hydrocarbon substrate to obtain an oxidation product which comprises the steps of contacting said hydrocarbon substrate with an unsupported, dissolved catalyst system which comprises palladium chloride components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
2. A process for olefin oxidation which comprises the steps of contacting said olefin with an unsupported, dissolved catalyst system which comprises palladium chloride components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
3. A process for olefin oxidation to ketones which comprises the steps of contacting said olefin with an unsupported, dissolved catalyst system which comprises palladium chloride components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
4. A process for the oxidation of a hydrocarbon substrate to obtain an oxidation product which comprises the steps of contacting said hydrocarbon substrate with a substantially chloride-free, unsupported, dissolved catalyst system which comprises palladium components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
5. A process for olefin oxidation which comprises the steps of contacting said olefin with a substantially chloride-free, unsupported, dissolved catalyst system which comprises palladium components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
6. A process for olefin oxidation to ketones which comprises the steps of contacting said olefin with a substantially unsupported, dissolved catalyst system which comprises palladium components, copper components and a nitrile ligand in the presence of oxygen, and separating the oxidation product from said catalyst system.
7. A process according to claims 4, 5 or 6 wherein the palladium component is a palladium salt, PdX2, the copper component is a copper salt, CuY2, wherein X and Y are counterions independently selected from the group of counterions consisting of BF4 -, CF3 COO-, CH3 COO-, SO4.sup.═, and NO3 -.
8. A process according to claims 4, 5 or 6 wherein the palladium component is Pd(BF4)2, the copper component is Cu(BF4)2 and the ligand is acetonitrile.
9. A process according to claims 4, 5 or 6 wherein the palladium component is Pd(CF3 COO)2, the copper component is Cu(CF3 COO)2 and the ligand is acetonitrile.
10. A process according to claims 4, 5 or 6 wherein the palladium component is Pd(CH3 COO)2, the copper component is Cu(CH3 COO)2 and the ligand is acetonitrile.
11. A process according to claims 4, 5 or 6 wherein the palladium component is Pd(SO4), the copper component is Cu(SO4) and the ligand is acetonitrile.
12. A process according to claims 4, 5 or 6 wherein the palladium component is Pd(NO3)2, the copper component is Cu(NO3)2 and the ligand is acetonitrile.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000536A1 (en) * 1988-07-13 1990-01-25 Catalytica, Inc. Process for obtaining substantially aldehyde-free ketone products
CN103055907A (en) * 2013-01-25 2013-04-24 华东理工大学 High-water resistance catalyst for low-temperature oxidization of CO (Carbon Monoxide) and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850980A (en) * 1960-09-28 1974-11-26 Ici Ltd Production of esters
US4155879A (en) * 1976-09-30 1979-05-22 Institut Francais Du Petrole Process for manufacturing supported bimetallic catalysts useful for the heterogeneous phase oxidation of olefins to ketones
US4605776A (en) * 1984-01-27 1986-08-12 Babcock-Hitachi Kabushiki Kaisha Process for producing acetone
US4620038A (en) * 1984-02-29 1986-10-28 Babcock-Hitachi Kabushiki Kaisha Process for producing methyl ethyl ketone

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3850980A (en) * 1960-09-28 1974-11-26 Ici Ltd Production of esters
US4155879A (en) * 1976-09-30 1979-05-22 Institut Francais Du Petrole Process for manufacturing supported bimetallic catalysts useful for the heterogeneous phase oxidation of olefins to ketones
US4605776A (en) * 1984-01-27 1986-08-12 Babcock-Hitachi Kabushiki Kaisha Process for producing acetone
US4620038A (en) * 1984-02-29 1986-10-28 Babcock-Hitachi Kabushiki Kaisha Process for producing methyl ethyl ketone

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990000536A1 (en) * 1988-07-13 1990-01-25 Catalytica, Inc. Process for obtaining substantially aldehyde-free ketone products
CN103055907A (en) * 2013-01-25 2013-04-24 华东理工大学 High-water resistance catalyst for low-temperature oxidization of CO (Carbon Monoxide) and preparation method thereof

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